Carbohydrate processes



P 2, 1952 j K. M. GAVER 2,609,368

CARBOHYQBIATE EROCESSES Filed; Oct. 21.- 195p GLUCOPYRANOSE -ALKALI METAL ALCOHOLATE IN POLYMERS NON-AQUEOUS'ALCOHOLIC SOLVENT HEATING 80-ll5 G.

2-MONOALKALI 'GLUCOPYRANOSE POLYMERS INORGANIC 8- METAL) ORGANIC REACTANT SALT Z-MONO-INORGANIC Z-MONO-ORGANIC (asiMETAl-l-lc) GLUCOPYRANOSE POLYMERS GLUCOPYRANOSE POLYMERS IN V EN TOR.

A TTORNEY Patented Sept. 2, 1952 UNITED STA S PATENT i.

' Kenneth M. Gaver, Columbus,.0hio, assignor to Y The, hio.State University Research Founda jtion, Columbus, Ohio, a. corporation of Ohio 1 Application October 21, 1950, Serial No; 191,449

The inventions disclosed in this application relate to new. processes for thev formation of 2-substituted glucopyranose polymers. .The processes described herein illustrating my invention are designed to produce products. ,from (cellulose, starches, dextrins and similarlmaterials.

This application is in partYaicontinuation of my copending application .Serial ,No.i 792,826, filed December. 19, 1947, now abandoned and in part .a continuation'of the subject matter disclosed in copendingapplication Serial No. 694,328, filed August 31, 1946. l .The inventions described herein are designed to produce products like the new products disclosed in my Patent"No. 2,518,135. I have discovered a new-methodby which the 2-substituted alcoholates of glucopyranose polymers described in said Patent No.2,518-,135 may be prepared. This process is applicable to all types of glucopyranose polymers, including cellulose, starches, dextrins and similar materials. This method consists of the reaction of glucopyran'ose polymers with an alkali; metal alcoholate in a nonaqueous alcoholic system at a temperature of from 80 C. tolaboutlllfi" C.

I have found that not onlyciellulose proper but also such materials as, oxycellulose, hydrocellulose and lichenin act similar in my processes. I, therefore, include such materials in the term ffcellulosic materials and define for the purposes of'this specification the term cellulosic materials to include oxycellulose, hydrocellulose, hemicellulose and lichenin as well as true celluuse, All of these compounds where manipulated according to my processesreact'similarly; The processes when applied to cellulosic materials as above defined ordinarily include the synthesis of a monoalkali cellulosic-material by reaction of the cellulosic materials'with an alkali metal hydroxide in a nonaqueous solution at a temperatureof from about 80-'-81 Q. or higher.

The processes described herein apply also to the treatment of starches and dextrins of all kinds. In the treatment of ,all glucopyranose polymers, including cellulose, starches and dextrins, these new processes have the advantage over the process described in Patent No. 2,518,135 in that while in the patented; process water is formed .by the reaction between the glucopyranose polymer; and the alkali metal hydroxide which-- tends to dilute the suspensionand to slow :up the reaction,-in this new processno water is formed but instead the reaction produces an alcohol which serves as a-solvent for theprocess.

1 :Prior to my discoveries, the methods normally used for the treatment of cellulose with alkali metal-were the mercerization process and the processes (as described by Scherer and I-I ussey, fichorigin, Peterson-;and= Barry, and Muskat) in 14 Claims. (01. 260-209) which the cellulose is reacted with an-alkali metal in ammonia. In this last namedprocess'Q(depending upon the amount ofalkali metal present) the reaction produced'a' mixture of monosubstituted cellulose and polysubstituted cellulose or a cellulose which was substantially completely substituted (1. e. a polysubstituted cellu-' lose). In" such mixtures, itkwa's' impossible to predetermine or control the "positions on which thealkali metal would be substituted norwas it possible to obtain a pure monosubstituted cellu- 1086- v l .7

While Schinid and others re'ported that glycol,

glycerin, glucose, glycogen, inulinand starch reacted readilyin liquid ammoniawith metallic sodium to give exclusively 'a monometallic derivative, Scherer and' Husseyshowedthat when cellulose was allowed to reactwitli an excess of sodium and liquid ammoniafa trisodium cellulosate was formed. Moreover, Schorigin et' al. found that when sodium andcellulose were, reacted in liquidammonia all of the availableliy droxyl groups were afiected byT'the reaction. They reported thatthe reaction was continuous rather than stepwise andthat there isno preferential action between' the metallic sodium and any (particular hydroxyl groupl Peterson and Barry reported that when anhydrous cellulose is suspended in'li'quid ammonia and treated with alkali metal, there is readily produced an alkali metal cellulosate, the reaction being substantially quantitative up to the production of the trimetallic cellulosate.

Inthe customary method of mercerizing cotton and other cellulose to form a hydrocellulose, cotton has usually been treated with sodium-hydroxide in'the form of a concentrated (15-25% V or higher) aqueous solution. This causes the cotton to shrink, become heavier, denser and stronger and acquire a milky lusterz. In this process, the metal does not enter the molecule but merely forms an addition product. Treatment of cellulose with dilute sulphuric acid also forms a hydrocellulose while dilute nitric acid' forms'an oxycellulose. Hydrocellulose and oxycellulos may be formed in various other ways; v V

, In the preparation of cellulose ethers,' cellulose has been treated with sodium hydroxide "or equivalent alkali eitherin the. form of a concentrated-aqueous solution or'by mixing the'fcellulose withisolid sodiumlhydroxide'i'n the presence of'sufiicient .water to dissolve all of the alkali. Thev alkali cellulose soforined isLmerel'y an addition product. The alkaliflcelluloseaddition product-s'o formed may beisubjected, to. the action of an etherifying agent such as arialkyl halide, an alkyl sulfate, an aralkyl halide, or'other'inorganic esters of alkyl or aralkyl alcohols or the like, pref- O FiCE-Y point of ammonia, and to follow this step without isolation of the product by treatment with a f i etherifying agent. As stated above, with all or" tion of the reaction.

Dextrins, as is well known, are carbohydrates usually produced by hydrolysis of starch and are intermediate products between starchesv and the sugars.

However, it is Well known that starch on the one: hand and the sugars and cellulose on the other have altogether different reactions when mixed with metallic alkali in liquidammonia. As statedabove, Schmidet al. stated that when inulin, starch and glycogen were reacted in liquid ammonia. withmetallic'sodium, they gave an exclusivelymonometallie derivative and Scherer and Hussey,and sc-horigin" et' al. showed that when cellulosewa'sallowed toreaet with an excess of sodium: in, liquid ammonia, allavailable hydroxyl groups reacted to form a trisodium'cellulosate. Muskat reported that potassium in liquid ammonia reactsgcompletely with all of the available hydroxyl groups-19f the simple sugars and their substitutionprodu'cts; When treated with an alkali metal in"1iuuid' fammonia; dextrins, depending on, their molecular -weight, behave sometimes assugars andsometimes; as starches.

I have now-discovered, that when cellulosic material, starches and de xtrins are reacted with an alkali metal alcoholatein'a substantially nonaqueous alcoholic solvent, a monoalkalisubstituted product is formed.- -'Ihat is to say, I have now discovered that, when" glucopyranos e polymers, including cellulosic material, starches and dextrins (havingthe glucopyranose units polymerized to an extent of atleast ten'units per molecule) are reacted with an alkali: metal alcoholatein a ngnaqueous solvent at a temperature of from. 80-'8-I Q. or; higher up to about 115 C., the alkali metal'is substituted for the hydrogen of the most acidic hydroxyl group to forma monosubstituted glucopyranose polymer in which the alkali metal replaces the hydrogen of the No. 2 hydroxyl unit of substantially all of the glucose units of the cellulosic material, starch or dextrin (i. e. the hydroxyl group which'is next adjacent to the carbonyl group of each glucose unit) to form a 2-alkali metal glucopyranose polymer (cellulosate, starohate or substituted dextrin) in pure form. 1

When dextrins are reacted with an alkali metal dissolved in liquid ammonia, the, reaction depends on the type of dextrin. In some cases inliquid ammonia, all of the hydrogens of all of the free hydroxyl groups are reacted tov form polysubsti tuted alkali dextrins. In other-cases, only one ofthe free. hydroxyl groups may be'afiected. The reaction ranges from areaction similar to" that of the sugars to a reaction similar to thatof the starches but as stated above where the, reaction is, induced by moderate heating with a nonaqueous aloolf olie solution ofalkali metal alco- ,holate, onlygone hydroxylgroup is reacted. Preferably, I form my dextrins by the hydrolysis of starches by one or more, of. the usual methods.

Then I' alkalate'the dextrin' 'so'iormed' by the substitution of an alkali metal in place of the 10. such methods it is impossibleto, control the posi- I 4 hydrogen of the most acidic hydroxyl group of the glucopyranose units of the dextrin.

I have found that by the Williamson reaction, any such z-substituted alkali metal glucopyranose polymer may be converted to a 2-organic glucopyranose polymer, or glucopyranose ether. In fact, I may substitute for the alkali metal any other desired atom or radical (having a valence 'of one) as, for example, metal salt and other desired suitable inorganic reagents to obtain any desired substituted; inorganic glucopyranose product. 'I can thereafter further hydrolyze the substituted glucopyranose polymer to obtain a substituted sugar. Especially substituted dextrins are useful as intermediate products in formin desirable substituted sugars. They are also useful in modifying and improving the characteristics of dextrinadhesives. M l

It is anobject: therefore of: my invention to. provide new and useful; processes of forming monosubstituted glucopyranose polymers.

It is a iurtherobj ectofmy invention to provide. a new process of reactingglucopyranose polymers; with alkali metal alcoholates.

It is a iurtherobject-oi my invention to provide. a new method cr -formingnonaqueous'alkali metal substituted"glucopyranose polymers and of absorbing any Water which iseither initially present or which is formed by the-reaction.

Further object's comprise the provision. of new methods for the formation of'2emonosubstituted glucopyranose polymers including 2emonosubstituted cellulosate's, 2-monosubstituted starchates and Z-monosubstituteddextrins.

Further objects and features ofthe present invention will be apparent from the following description, reference being: had to the accome panying drawings wherein preferredv forms of embodiments of the invention are clearly shown-v In the drawings? 1? i Fig. lis aflowsheet disclosing a method of forming 2-monoalkali glucopyranose polymers, 2-monoorganic glucopyranose olymers, Z-monometallic glucopyranose polymers, and 2-monononmetallio inorganic glucopyranose polymers.

In general, the inventions" disclosedherein are illustrated by processes of forming 1) a 2-monoalkali ce'llulosa-te, a 2-monocellulose ether, and a 2-monometallic cellulosate; (2 a 2-monoalkali starcliat'e, a 2-monometal-lio starchate, and a 2'- monoalk-yl starchate, and- (-3 a.2-monoalkali dextrin, a z-monoalky-l dextrin and a 2-monometallic dextrin. For example, cellulose may be first treated with a;substantially nonaqueous solution of an alkali metal alooholate at a temperature of from -8? (3. or higher up to about 1 15 C. so that the alkali metal aleoholate reacts with the glucose residueuhitsoi thecellulose to replace by the alkali metal the hydrogen of the hydroxyl group-next adjacent tothecarllonylgroup thereof soas to form a 2-mono'alkali 'cellulbsate. This 2- monoalkali cellulo'sate-is then reacted with an alkyl halide or similar organic reaotantto substitute an organic group-in place of the alkali metal of the cellulosate to i orm a cellulose ether organic cellulosate) in; which-"the organic group is attached in all cases to the number two carbon atom (i. e. the-carbon atom next "adjacent: to the carbonyl group). Alternatively-the 'monoalkali cellulosate may bereacted with a metal or other inorganic salt to form a metal or other inorganic cellulosate.

Also when a starch or a dextrinis treated with an alkali metal alcohol'ate iiisolution ina substantially nonaqueous solviantat a temperature of from 80 C., a mono-alkali substituted starcha'te or dextrin is formed in which the alkali metal is substituted for the hydrogen of the No. 2'carbon (which is the most acidic hydroxyl group) to form the 2-monosubstituted starch-ate or dextrin. These monosubstituted starchates and dextrins may then be reacted with alkyl halides or similar organic reactants to substitute an organic group in "place of the alkali metal of the substituted 'starchat'e or dextrin to form analkyl starchate or dextrin ether in which the organic group is attached in all cases to the No. '2 carbon atom (i. e. the carbon atom neXt adjacent to the carbonyl group). Alternatively the monoalkali s-tarchate or dextrin may be reacted with a metal or other inorganic salt to form a. metal or other inorganic starchate or substituted dextrin.

In preparing the 2-monoalkali glucopyrano-se polymers, the 2-mono-organic glucopyran'ose polymers and the z-monoinorganic gluc'opyranose polymers referred to above, we have investigated the effect of the following factors on the reaction.

NATURE OF SOLVE'NT The solvent must be substantially nonaqueous and is preferably alcoholic. It is found that any of the following alcohols may be used, provided that certain other variables are sufiiciently controlled. It must be understood, however, that not all solvents mentioned have the-same utility in the process. It must also be understood that any other nonaqueous solvent which will dissolve the alkali even in small amounts is a suitable vehicle in which to carry out the reaction provi-ded that certain other variables are sufficiently controlled. Following is .a list'of alcohols which have been found to be satisfactory:

Alcohols which may be used allyl dimethyl isopropyl cariso-amyl binol n-amyl di-n-propyl carbinol sec.-amyl di-iso-propyl carbinol tert.-amyl ethyl anisyl Z-ethyl butyl benzhydrol 2-ethyl hexanol benzoylcarbinol furfuryl benzyl n-heptyl 2,3-butanediol n-hexyl n-butyl sec.-hexyl iso-butyl lauryl I see-butyl methallyl tent-butyl methyl sec. butyl carbin-ol methyl amyl 5(p-tert. butyl phemethyl butyl earbinol noxy) ethyl o-methyl cyclohexanol capryl m-methyl cyclohexanol ceryl p-methyl cyclohexanol cetyl Z-methyl pentanol-l dimethyl n-propyl calf:

binol methyl isopropyl carbinol n-nonyl n-octyl oc-tanol-2 phenyl-propyl n propyl iso-propyl tetrahydrofurfuryl I triethyl oarbinol triphenyl carbinol 6 .Vw'io o yhy r c a o o s. wh h .may clsob e used ethylene glycol 5 ethylene-' glycol r'nonomethyl ether ethylene glycol monoethyl-ether ethylene glycol monobe'nzyl ether ethylene glycol monobutyl ether diethylene glycol diethylene glycol monomethyl ether diethylene glycol monoethyl ether diethylene glycol monobenzyl ether diethylene glycol monobutyl ether di-propylene glyc glycerol glycerol q-n butylether I glycerol ea -dimethyl ether glycerol ayy' diphenyl ether glycerol -monomethyl ether hexamethylene glycol I 2-methyl-2,4-pentanediol propylene glycol triethylene glycol trimethylene glycol It is clear therefore that'all nonaqueous solvents capable of dissolving sodium" hydroxide to the extent of-0.04 N. or higher are satisfactory. Some of the lower'alcohols (suchas methanol and to a-lesser extent' ethanol, propanol, etc.) which readily 'give'up a hydrogen ion in solution are not satisfactory with. all typestoflalkali because of therelatively high acidity of such alcohols.

TEMPERATURE Any temperature from -810 C. up to about C. in an open or closed system produces a 2-monoalkali product. Somewhere above about 115 C. a reaction occurs on the No. 3 carbon atom and in such "cases the product is no longer a 'monoalkali product. Ihis monoalkali reaction can be'drive'n to completion at temperatures somewhat lower than 80- 0. However, under usual' operating conditions, the raising of the temperature -'up to about 80-81 C. is one of the most'important considerations.

PRESSURE Apparently there is but very slight volume change occurring in the monoalkali reaction. Pressures up to about 55 lbs. have been used with no effect on the course of the reaction or upon the product produced by the reaction. It is very probable that any pressure may be used provided the temperature and other requirements are met. v

' time: OF REACTION CONCENTRATION 7 :It has-been repeatedly demonstrated that at temperatures under the temperature of 115 C.,

the reaction is independent of alkali concentration and the same produot is always obtained provided there is i'sufiicient' alkali present to satisfyv the requirements of theproduct. At the lower temperaturel rangeltil e'.- 80 0.), it .is. ad'- visable to-use an excess of alkali in order to complete the reaction within a two hour period. At the higher temperature range (i. e., 81-1l5 0.), only the amount, of alkali approaching the stoichiometric equivalent is necessary or desirable. The mother liquor-from the latter reaction always shows a faint alkalinity of approximately 0.04 N.

NATURE OF THE ALKALI- All of the alkalizmetal alcoholates yieldsimilar products. For example, sodium methylate, sodium propylate; and sodium butylate all yield chemically similar products. Any alkali metal alcoholate having an ionization constant of 2 1O or greater will react provided that it is more than very slightly soluble in the chosen reaction solvent and also provided that the; molecular size of the reaction molecule. is not too large to locate itself to react with the glucopyranose polymer.

NATURE OF THE GLUCOPYRANOSE lhe c'arbohydric. material which is to be treated may be an'ycarbohydrate or: similar material in which there is av hydroxyl'or similar group positioned on the carbon which is adjacent to a carbon atom forming a part of. a carbonyl group. For example, celluloses,vv starches. 'dextrins, dextrans, sugarshexosans, pentosans. and mixed hexosans' and p'entosans are usable. Various kinds of these classes are usuable, as for example, the various kinds of celluloses, starches and dextrins set out below.

NATURE OF C'EILULOSE- sponding to a sodium hydroxide solution of 0.04 N or higher) at a temperature of 80 C. or higher (Wither without agitation); for a' period of two hours or longer. In such cases a reaction will occur on the second carbon atom which will go practically to completion provided alkali is present in sufficient quantity to permit one mole of alkali to react with one mole (162 grams) of cellulosic material. Under certain described exceptions the temperature may be 80 C. or'lower, and under other described conditions the time may be under two-hours.

If. desired. true cellulose may be first treated (as with sodium hydroxide). to produce a hydrocellulose or firsttreated (as with dilute nitric acid) to producean oxycellulose- The liy'clrocellulose or the oxycellulose, as the case may be, may then be isolated. or purified as by washing, etc. and then treated exactly as decribed above and with; the; same limiting factors to transform it to a 2-morrosubstituted hydrocellulose or 2-monosubstituted oxycellulose as the case may be. Lichenin oraother hemicell'ulose may be-treated in. thesamermanner. and subject to the same limitations;as"desoribed' above to produce a 2- lnonosubstituted hemicellulose.

NATURE on e'rARcn ,NATURE on THE. DEXTRIN Similar products were prepared using potato, sweet potato, wheat. tapioca and corn dextrins. Moreoven'acid; alkali, heat converted, oxidative corn'dextrins enzymatically synthesized at, B- and y Schardinger dextrlns and many other dextrins have been used to? prepare similar products. Thus the various dextrins used varied in the size of the molecules from dextrins having molecules containing about ten glucopyranose' units to the molecule up to dextrins which have molecules of approximately the size of starch.

Generally in-the case of the acid converted corn dextrins, the" color becomes increasingly darker as conversion increases and as the number of free aldehyde groups increases.

LIIECHANISIVI OF THE REACTION etc. Thus by the use of the alcoholate, the water formed in the main reaction is removed by absorption to produce-more alcohol and alkali hydroxide,

FORMATION OF ETHERS Any such monoalkali glucopyranose polymers may be reacted'with any organic reactant (as for example an organic halide) to produce aZ-monoorganic glucopyranose polymer. To accomplish this object I treat the monoalkali with anotherifying agent (i. e., organic reactant)". I- may suspend the Z-mQnoorganic glucopyranose polymer for from'one to tenminutes in from one to ten times the calculated quantity of an etherifying agentand-heat(-with pressure if desired) to 81 "C. or higherie. gl, to 92 C.) for from two to twenty-iour'hours. By this operation 1-- obtain a monoorganic glucopyranose polymer which when the reaction is completed produces a 2- monoorganic glucopyrancse polymer each unit of which has a, formula of V O nocniomcinxcnonxcn'oroono) A dlSpBISiTlgSOIVGnt may be used as desired but is unnecessary. The reactants may be agitated or notes desired. Pressure may be applied or not as desired. The monoalkali gluoopyranose polymer may be treated with the organic comethers, thefollowing may bementioned.

acetodichlorohydrin i allyl bromide allyl chloride allyl iodide n-amyl bromidev iso-amyl bromide 1' iso-amyl chloride tert.-amyl chloride: amylene dichloridei' V iso-amyl iodide I 1 benzalacetophenone dibromide benzal chloride benzotrichloride benzyl bromide benzyl chloride bromoacetic' acid 7 e w-bromoaceto-B-naphthone a-bromo-n-butyric acid- 2-bromo-l-chloropropane bromocyclohexane' B-bromoethyl ether B-bromoethyl phenyl ether bromoform 2-bromo-n-octane bromophenacylbromide bromopicrin W a-bromopropionic acid fl-bromopropionic acid I -bromopropyl phenylether a-n-valeric acid a-bromo-iso-valericacid v-butyl bromide iso-butyl bromide sec.-butyl bromide I tert.-buty1bromide n-butyl chloride iso-butyl chloride sec.-buty lch1oride tert.-butyl chloride n-butyl chloroacetate V iso-butyl chlorocarbon'ate" a-butylene-bromide S-butylene bromide 1 iso-butylene bromide n-butylidene chloride n-butyl iodide iso-butyl iodide sec.-butyl iodide tert.-butyl iodide cetyl bromide cetyl iodide chloral T chloroacetamidei chloroacetodiethylamide chloroacetic acid chloroacetone chloroacetonitrile' chlorobutane fi-chlorobutyric acid; 'y-chlorobutyronitrile chlorocyclohexane l B-chloroethyl acetate p-chloromethyl chlorocarbonate 10 chloroform chloropicrin a-ChlOIOPIOIJiOIliC acid l3-chloropropionic acid fi-chloropropionitrile v-chloropropyl chlorocarbonate decamethylene bromide a,e-dibromobutyric acid 2,3-dibromopropene mfi-dibromopropionic acid .e

3,'y-dibromopropyl alcohol 3,5-dibromopyridine ap-dibromosuccinic acid dichloroacetic acid v, -dichloropropyl ether p,fi'-dichloroisopropy1 ether epibromohydrin epichlorohydrin ethyl bromide ethyl bromoacetate ethyl a-bromo-n-butyrate ethyl a-bromo-n-caproate ethyl bromomalonate ethyl a-bromopropionate ethyl fi-bromopropionate ethyl a-bromo-isovalerate ethyl chloride ethyl chloroacetate ethyl a-choloroacetoacetatev ethyl chlorocarbonate v ethyl B-chloropropionate ethyl dibromoacetate ethyl dibromomalonate ethyl diohloroacetate ethylene bromohydrin ethylene bromide ethylene chloride ethylene chlorobromide ethylene chlorohydrin ethylidene bromide I" ethylidene chloride" ethyl iodide ethyl trichloroacetate glycerol a,'y-dibromohydrin glycerol a,'y'-dichlor'ohydrin glycerol a,b -dichlorohydrin glycerol a-monochlorohydrin n-heptyl bromide n-heptyl iodide hexachloroethane hexamethylene bromide n-hexyl bromide n-hexyl chlorocarbonate n-hexyl iodide iodoacetic acid --iodoform lauryl bromide lauryl chloride methyl bromide i methyl bromoacetate methyl B-bromopropionate 1 phenacyl bromide phenacyl chloride n-propyl bromide isopropyl bromide n-propyl chloride isopropyl chloride propylene bromide propylene bromohydrin propylene chloride propylene chlorobromide propylene chlorohydrin s-tetrabromoethane s-tetrachloroethane tetrachloroethylene 1,1,2-tribromoethane tribromoethylene 1,2,3-tribromo-2-methyl propane 1,2,3-tribromopropane trichloroacetic acid trichloro-tert.-butyl alcohol 2,2,3-trichlorobutyric acid 1,1,2-trichlorethane trichloroethylene 1,2,3-trichloropropane triglycol dichloride trimethylen bromide trimethylene bromohydrin trimethylene chloride trimethylene chlorobromide trimethylene chlorohydrin triphenylchloromethane o-xylyl bromide m-xylyl bromide p-xylyl bromide o-xylylene bromide o-xylylene chloride and similarly reacting chemicals including especially the esters.

The alkali cellulosate may, if desired, be dispersed with the organic reactant in any suitable solvent. In addition to the solvents mentioned above as solvents for the alkali hydroxides, the following dispersing solvents may also be used:

sec.-amyl benzene n-octane tert.-amy1 benzene iso-octane benzene n-pentane n-butyl benzene petroleum ether sec.-butyl benzene propyl benzene tert.-butyl benzene tetraisobutylene cunene tetradecane cyclohexane toluene 2,7-dimethyl octane tri-isobutylene ethyl cyclohexane trimethyl butane heptane trimethylethylene hexane 2,2,4-trimethyl pentane hexadecane triphenyl methane ligroin o-xylene methyl cyclohexane m-xylene nonane p-xylene and various others.

The following ketones may also be used: acetone acetophenone anisolacetone benzalacetone benzophenone benzoylacetone diethyl diisopropyl ethyl phenyl ethyl undecyl methyl amyl 12 methyl butyl o-methyl cyclohexanone m-methyl cyclohexanone p-methyl cyclohexanone methyl ethyl methyl hexyl methyl n-propyl methyl iso-propyl and various others.

The following ethers may also be used:

allyl chloromethyl allyl ethyl dichloromethyl n-amyl diethylene glycol iso-amyl diethyl anethole ethyl butyl anisole ethylene glycol benzyl dibenzyl benzylmethyl ethylene glycol n-butyl benzyl diethyl n-butyl ethyl n-butyl phenyl phenetole 1,4-dioxane n-hexyl di-n-propyl n-propyl benzyl ethyl iso-propyl and various others.

By these various lists we do not mean to exclude any other solvents, organic reacting materials and other dispersing solvents.

Various metal and nonmetal inorganic glucopyranose polymers may also be synthesized starting with the alkali metal glucopyranose polymers prepared as set out above. For example, we can prepare the following substituted products:

(a) Aluminum chloroglycopyranose polymer by reaction with aluminum chloride in ether.

(12) Lead chloro glucopyranose polymer by reaction with lead chloride in ether.

(0) Arsenic chloro glucopyranose polymer reaction with arsenic chloride in ether.

((1) Barium bromo glycopyranose polymer reaction with barium bromide in alcohol.

(e) Bismuth chloro glucopyranose polymer 0 reaction with bismuth chloride in acetone.

(f) Cadmium bromo glucopyranose polymer by reaction with cadmium bromide in alcohol.

(g) Calcium chloro glucopyranose polymer by reaction with calcium chloride in alcohol.

(h) Calcium chlorate glucopyranose polymer by reaction with calcium chlorate in alcohol.

(2) Cerium nitrate glucopyranose polymer by reaction with cerium nitrate in alcohol.

(7') Chromium chloro glucopyranose polymer by reaction with chromium chloride in alcohol.

(lc) Cobalt chloro glucopyranose polymer by reaction with cobalt chloride in alcohol.

(Z) Copper chloro glucopyranose polymer by reaction with copper chloride in alcohol.

(m) Iron chloro glucopyranose polymer by reaction With iron chloride in ether.

(n) Iron perchlorate glucopyranose polymer by reaction with iron perchlorate in alcohol.

(0) Lead aceto glucopyranose polymer by re.- action with basic lead acetate in alcohol.

(p) Magnesium chloro glucopyranose polymer by reaction with magnesium chloride in alcohol.

(q) Magnesium aceto glucopyranose polymer by reaction with magnesium acetate in alcohol.

(1') Manganese chloro glucopyranose polymer by reaction with manganese chloride in alcohol.

(s) Mercuric chloro glucopyranose polymer by reaction with mercuric chloride in alcohol.

(1?) Nickel chloro glucopyranose polymer by reaction with nickel chloride in alcohol.

aeoases (u) Phosphorus dichloro glucopyranose polymer by reaction with phosphorustrichloride in ether.

(22) Platinum chloro glucopyranose polymer by reaction with platinum chloride inether.

(w) Silver glucopyranose polymer by reaction with silver nitrate in'alcohol. Y

Stannous chloro glucopyranose polymer by reaction with stannous chloride in alcohol.

(y) Stannic chloro glucopyranose polymer by reaction with stannic chloride in ether.

(.2) Strontium bromo glucopyranosepolymer by reaction with strontium bromide in alcohol.

(aa) Thorium chloro glucopyranose'polymer by reaction with thorium chloride in alcohol.

(bb) Zinc chloro glucopyranose polymer by reaction with zinc chloride in alcohol.

(cc) Uranium glucopyranose polymer by reaction with uranyl acetate in alcohol.

Following is a list of some additional salts which when reacted with our monoalkali glucopyranose polymer produce metallic, nonmetallic or other derivative glucop'yranose polymer by double decomposition: aluminum bromide; aluminum iodide; aluminum nitrate; antimony chloride; antimony iodide; arsenic fluoride; arsenic iodide; arsenic sulfide; barium perchlorate; barium thiocyanate; beryllium bromide; beryllium chloride; beryllium fluoride; beryllium iodide; boron bromide; pcadmium iodide; cadmium nitrate; cadmium sulfate; calcium bromide; calcium perchlorate; calcium chromate; calcium iodide; calcium nitrate; calcium thiocyanate; cerium bromide; cerium iodide; chromium bromide; chromium fluoride; chromium nitrate; chromium sulfate; cobalt bromide; cobalt chlorate;'cobalt perchlorate;- cobalt iodide; cobalt nitrate; cobalt sulfate; cobalt sulfide; columbium chloride; columbium fluoride; copper bromide; copper fluoride; copper nitrate; dyspromium chloride; dyspromium bromide; dyspromium iodide; dyspromium bromate; erbium chloride; erbium nitrate; gallium sulfate; germanium bromide; germanium chloride; gold bromide; gold chloride; gold cyanide; indium perchlorate; indium nitrate; radium bromide; uridium bromide; iron bromide; iron iodide; iron nitrate; iron sulfate; iron thiocyanate; lanthanum bromide; lanthanum chloride;"lanthanum nitrate; lead chlorate; magnesium bromide; magnesium chlorate; magnesium iodide; magnesium nitrate; 'magnesium sulfate; magnesium thiosulfate; manganese nitrate; manganese sulfate; manganese sulfide; manganese thiocyanate; mercury ammonium iodide; mercury potassium cyanide; molybdenum chloride; neodymium chloride; nickel bromide; nickel perchlorate; nickel iodide; nickel nitrate; nickel sulfate; osmium chloride; phosphorus chloride; phosphorus oxychloride; phosphorus sulfide; phosphorus thiocyanate; platinum bromide; platinum sulfate; praseodymium chloride; radium bromide; radium chloride; rhodium chloride; ruthenium chloride; samarium chloride; selenium oxyfiuoride; silicon fluoride; silver perchlorate; strontium chlorate; strontium chloride; strontium sulfide; sulfur monochloride; tantalum bromide; tantalum chloride; terbium chloride; thallium bromide; thallium chloride; thallium iodide; thionyl chloride; thorium nitrate; tin iodide; titanium bromide; titanium chloride; tungsten bromide; tungsten chloride; uranium chloride; uranium nitrate; uranyl chloride; uranyl nitrate; vanadium bromide; vanadium chloride; vanadium fluoride; vanadyl sulfate;

yttrium bromide; yttrium chloride; yttrium iodide; yttrium nitrate; zinc bromide; zinc iodide; zinc nitrate; zinc thiocyanate; zirconium chloride; zirconium bromide; ziroonyl chloride;

Erample I Amounts of Q 200 gms. of wheat dextrin and 900 ml. of butanol were mixed together thoroughly and there were added to the mixture 68 gmsxof sodium ethylate.

This mixture was heated to C. for two hours. The reaction equation was Starch+sodium ethylate sodium starchate .+ethanol The ethanol was distilled out of the mixture leaving the sodium starch suspended in the butanol. The sodium starch was further reacted without purification. If desired, it could be filtered, from the butanol, washed and dried.

Example If A mixture of 200 gms. of corn starch and 900 ml. of butanol was mixed thoroughly and warmed to 50 C. There was added 96 gms. of sodium butylate. Heating was continued with agitation until the temperature reached about C. The reaction mixture was then cooled to 6 0" C. and further reactants were added without purification of the sodium starchate thus produced.

EwampZe III A mixture of l 200 gms. of wheat starch,

900 ml. glycerol, and 11 4 gms. of sodium g'lycerate was stirred and slowly warmed until the mixture thickened and the heating cautiously continued until a temperature of 95 C. was reached. An equal volume of butanol was added and the reaction product separated by filtration.

Example V A mixture of 200 gms. cellulose and 900 ml. butanol was warmed to 50 C. and there was added 54 gms. sodium methylate. Heating was continued until .the temperature reached 95 C.. The reaction equation was cellulose+sodium methylate sodium j cellulosate-imethanol As the reaction proceeded, ,methanol was produced and as'the temperature rose the methanol was removed from; the-system by distillationv so 115 as not to interfere withthe course of the reaction." 1 "1" Example V A reaction mixture of 200 gms. of thin boiling wheat starch, 1500 mls. absolute ethanol, and 160 gms. sodium ethylate starch-l-sodium ethylate monosodium starchate+ ethanol Example VI A mixture of 200 gms. of thin boiling corn starch, 1200 ml. anhydrous propanol, and 82 gms. sodium propylate was heated to boiling and the boiling continued for two hours. The mixture was cooled and the product reacted further without purification. It could be separated by filtration if desired.

Example VII A mixture of 200 gms. of corn starch, 1500 m1. of n-amyl alcohol, and 200 gms. of sodium butylate was prepared. This mixture was heated slowly under distillation and efficient agitation for one hour at 130 C. during which time the butanol formed in the reaction was distilled 01?. In performing this process, the course of the reaction may be determined by the amount of butanol recovered. Normally, one hour is satisfactory for the reaction but if the reaction has not proceeded satisfactorily, the heating period may be extended. v

The reaction mixture was filtered hot and washed with a minimum of hot, dry, n-amyl a1- cohol and then reacted as desired. The di-sodium starchate, thus produced, is not very stable in the dry state and should be made only as needed. g

It is to be understood that the above-described embodiments of my invention are for the purpose of illustration only and various changes may be made therein without'departing from the spirit and scope of my invention. I

Iclaim: 7

1. A process of producing cellulosates which comprises the reaction of a cellulosic material with a nonaqueous alcoholic solution of an alkali metal alcoholate at a temperature of from about 80 C. to about 115 C.

2. A process of producing a cellulosate which comprises the reaction of a cellulosic material with a substantially nonaqueous alcoholic solution of sodium methylate in equimolar quantities at a temperature of from about 80 C. to about 115 C.

3. A method of making an alkali metal cellulosate from cellulose comprising dissolving an alkali metal alcoholate in a substantially nonaqueous alcohol; adding the solution to a cellulose; and refluxing the mixture at a temperature of from about 80 C. to about 115 C.

4. A process. of treating cellulosic materials which comprises mixing said materials with a substantially nonaqueous alcoholic solution of an alkali metal alcoholate with the cellulosic material andthe alkaline metal alcoholate supplied in approximately equimolar quantities; and heating to a temperature of from about C. to about C.

5. A process of producing substituted glucopyranose polymers which comprises the reaction of glucopyranose polymer with a nonaqueous solution of an alkali metal alcoholate at a "tem' perature of from about 80 C. to about 115 C.

6. A process of producing a starchate which comprises the reaction of starch with a nonaqueous alcoholic solution of an alkali metal alcoholate at a temperature of from about 80 C. to about 115 C.

7. A process of producing substituted dextrins which comprises the reaction of dextrin with a nonaqueous alcoholic solution of an alkali metal alcoholate at a temperature of from about 80 C. to'about 115 C.

8. A process of producing a glucopyranose polymer which comprises the reaction of a gluco pyranose polymer with a nonaq'ueous alcoholic solution of sodium methylate in equimolar quantities at a temperature of from about 80 C. to about 115 C.

9. A method of making an alkali metal glucopyranose polymer from glucopyra'nose polymer comprising dissolving an alkali metal alcoholate in a substantially nonaqueous alcohol; adding the solution to a glucopyranose polymer; and re fiuxing the mixture'at a temperature of from about 80 C. to about 115 C.

10. A process of treating glucopyranose polymer which comprises mixing said materials with a substantially nonaque'ous alcoholic solution of an alkali metal alcoholate with the glucopyranose polymer and the alkaline metal alcoholate supplied in approximately equimolar quantities; and heating to a temperature of from about 80 C. to about 115 C.

11. A process of producing a cellulosate which comprises the reaction of a cellulosic material with a substantially anhydrous alcoholic solution of sodium methylate in equimolar quantities at a temperature of from about 80 C. to about 115 C.

12. A method of making an alkali metal cellulosate from cellulose comprising dissolving an alkali metal alcoholate in a substantially anhydrous alcohol; adding the solution to a cellulose; and refluxing the mixture at a temperature of from about 80 C. to about 115 C.

13. A process of treating cellulosic materials which comprises mixing said materials with a substantially anhydrous alcoholic solution of an alkali metal alcoholate with the cellulosic mate'- rial and the alkaline metal alcoholate supplied in approximately equimolar quantities; and heating to a temperature of from about 80 C. to about 115 C.

14. A process for producing substituted glucopyranose polymers which comprises the reaction of glucopyranose polymer with a nonaqueous alcoholic solution of an alkali metal alcoholate at a temperature of from about 80 C. to about 115 C. with the glucopyranose polymer and the alkali metal alcoholate supplied in approximately equimolar quantities.

KENNETH M. GAVER.

(References on following page) 17 REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,094,100 Dreyfus Sept. 28, 1937 2,181,919 Scherer Dec. 5, 1939 2,294,924 Miller Sept. 8, 1942 18 Number Name Date 2,300,413 Gaver Nov. 3, 1942 2,389,771 Gaver Nov. 27, 1945 2,397,732 Gaver Apr. 2, 1946 2,518,135 Gaver -1. Aug. 8, 1950 OTHER REFERENCES 7 Organic Chem, Fieser & Fieser, 1944, pages 

5. A PROCESS OF PRODUCING SUBSTITUTED GLUCOPYRANOSE POLYMERS WHICH COMPRISES THE REACTION OF GLUCOPYRANOSE POLYMER WITH A NONAQUEOUS SOLUTION OF AN ALKALI METAL ALCOHOLATE AT A TEMPERATURE OF FROM ABOUT 80* C. TO ABOUT 115* C. 